Insecticidal composition



Patented June 20, 1944 UNITED STATES PATENT OFFICE INSECTICIDAL COMPOSITION Gerald B. Coleman and Clarence L. Moyle, Midland, Mich, asslgnors to The Dow Chemical Company, Midland, Michigan Mich, a corporation of No Drawing. Application July 21, 1940,

Serial No. 348,010

8 Claims.

- quitos, and common agricultural insect pests.

Extracts 'of such insecticidal plant products as pyrethrum flowers, derris, cube, timbo, barbasco, and the like are widely used for the control of insect pests.

These toxicants are generally employed as constituents of dusting mixtures, in petroleum distillate sprays, or in aqueous dispersion. Pyrethrin-containing compositions have quick paralyzing action on flies and. other insects but glve a relatively low kill as compared to the per cent knockdown. With rotenone, a high moribund" kill is generally obtained, although a considerable period of time is required to destroy insect pests. The plan extracts generally are unstable to light and heat and lose their effectiveness to a considerable degree upon storage.

We have discovered that certain thio-ether compounds are effective substitutes for extracts of insecticidal plant products. This group of compounds is characterized by the following formula wherein It represents a cyclic organic radical selected from the group consisting of aromatic, alicyclic, and heterocyclic radicals, X represents chlorine or RS, n is an integer from 2 to 4, inclusive, and m is an integer not greater than 3. These compounds are more stable to heat, light, and air than are pyrethrin and rotenone. Dust and spray compositions containing these compounds as sole toxic ingredients compare favorably in insecticidal efficiency with analogous compositions comprising the plant extracts. Furthermore, small amounts of the thio-ethers may be used to fortify compositions comprising insecticidal plant products whereby improved insecticidal materials are obtained which are more stable to heat and light and have a greater paralyzing effect and greater lethal-eflect on insects than do the original extract-containing composi. tions. By employing these ether compounds to fortify and supplement the action of such known insecticidal materials, an increased efliciency is obtained and economies in the amounts of py rethrin and rotenone required are effected.

when the thio-ethers are used alone, a concentration of from about 2 to 10 per cent by weight in the spray or dusting composition is satisfactory. For use in fortifying compositions pound is preferably employed in amount of from about 0.5 to 5 grams per 100 grams of the composition.

The thio-ethers with which the present inven- 5 tion is concerned are conveniently prepared by' reacting the dichloropolyalkyl ethers with the thiophenols, thiocycloalkanols, and heterocyclic mercaptans in the presence of aqueous sodium hydroxide. In carrying out this reaction an excess of the dichloro ether is reacted with substantially equimolecular proportions of the caustic and sulfur-containing compound. The various reactants are mixed with water and heated to a reaction temperature generally between about 90 and 125 C. with stirring. When the reaction is complete, the mixture is cooled, washed with water, and the desired compounds obtained by fractionally distilling or by other method of separation. If desired the oily product of reaction can be separated from the reaction mixture by decantation and used for insecticidal purposes directly or after unreacted dichloro-ether has been removed by distillation. Both the monoand disubstituted derivatives of the dichloro-polyalkyl ether are generally produced in the reaction. The mono-substitution product is obtained in good yield when appreciable excesses of the dichloro ether are employed.

The method employed in determining the in '30 secticidal toxicity of the spray compositions disclosed in certain of the following examples is substantially that described in Soap 8. No. 4, 1932,

and known as the Feet-Grady method. For purpose of comparison a pyrethrin solution consist,-

ing of the extractable toxicants from one poundof pyrethrin flowers dissolved in one U. S. gallon of a petroleum distillate having a boiling range of 345-508 F. and a flash point of 137 F. was employed as a control. I

The following examples are purely illustrative and are not to be construed as limiting:

Exwu: 1

In similar determination beta-(pheriylthioicomprising pyrethrins or rotenone, the ether combeta'whlom-diethyl ether. oiling at -130 C.

cent in 48 hours.

at 2 millimeters pressure and having a specific gravity of 1.173 at 20'l4' 0., gave a knockdown 1.133'at 25/4 C. gave a knockdown of 94 per cent in 10 minutes and a kill of 57 per cent in 48 hours.

In control determinations the pyrethrin-con taining control solution gave an average knockdown of 99 per cent in 10 minutes and akill of 53 per cent in 48 hours.

Exam? 2 The control pyrethrin composition was employed to prepare fortified fly spray mixtures in which the synthetic thio-ethers were incorporated as a supplementary toxicant. The control solution gave a knockdown of 99 per cent in 10 minutes and a kill of 36 per cent in 48 hours.

50 milliliters of this control solution was diluted with 50 milliliters of petroleum distillate, and 2.5 grams of beta-beta'-di-(phenylthio)-diethyl ether dissolved therein. When tested'according to the Feet-Grady method, this composition gave a knockdown of 99 per cent in 10 minutes and a kill of 82 per cent in 48 hours.

A'similar composition in which beta-(Z-benzothiazyl-thlo) -beta'-chloro-diethyl ether was em-' ployed as the addition agent, gave a knockdown of 99 per cent in 10 minutes and a kill of 61 per Emu: 3

The new group of toxicants may also be employed in aqueous dispersion for the control of such insects as the Colorado potato beetle, poplar aphis, and the like. A representative composition is as follows:

Composition A Beta- (fi-tertiarybutyl-2-benzothiazylthio) beta'-chloro-diethyl ether -pounds 3 Diatomaceous earth do 12 Sodium-lauryl-sulfate do- 0.5 Water gallons. 100

Dust compositions adapted to be employed for the control of pea-aphls have the following composition:

Composition B Composition Parts by weight Delta-delta'-di-(2.4.6 trichloro-phenylthio) dibutyl ether 3 Diatomaceous earth 97 Composition D Parts by weight Beta 1 naphthylthio) beta (ii-chloroethoxy)-diethyl ether 3.5 Red 96.5

and'- beta-(4-methyl-phenylthio) -beta"- assume Composition E Parts by weight Beta (cyclohexylthio) beta -chloro-diethyl ether Beta-(4-tertiarybutyl-phenoiw) -beta thio cyano-diethyl ether a 1 Diatomaceous earth 98 hmong other compounds which may be similarly employed are beta-(6-chloro z-benzothiazylthio)-beta-chloro-diethyl ether, betabeta'-di-(2-benzothiazylthio) -diethyl ether, beta- (6-phenyl-2 -benzothlazylthio) -beta-chloro dif ethyl ether, gamma '(6 cyclohexyl 2 benzothiazylthio) -gamma'-'chloro-dipropyl ether, beta- (2-benzothiazylthio) -beta'-(2-chloro ethoxy)- diethyl ether, beta-(2-phenylthioethoxy) -beta' (2-chloroethoxy) --diethyl ether, delta-delta'-di-'- (4-chloro-2 methyl-phenylthio) dibutyl ether, beta- (3-methyl-cyclohexylthio) -beta'-chlorodiethyl ether, beta-(3-mercapto-5-thiadiazylthio) beta'-chloro-diethyl ether, beta-(1-phenyl-5- tetrazylthio)-beta'-chloro-diethyl ether, beta- (2-allyl-amino-5-thiadiazylthio)-beta' chlorodiethyl ether, beta-(4-oxo-2-thiazylthio) -betachloro-diethyl ether, beta-5-cyclohexylidene-4- oxo-2-thiazylthio)-beta'-chloro diethyl ether, beta- (Z-benzimidazolylthio) -beta-chloro-diethyl ether, etc. v i

The new thio-ethers with which the present invention is concerned may be used also as toxicants in emulsions and in combination with soap or other wetting, emulsifying, or detergent agents. Various perfumes or coloring agents may be employed therewith if desired. Besides petroleum distillates, other organic solvents such as benzene, ethylene chloride, hydrogenated naphthalene, butyl alcohol, ketones, etc. 'may be employed. The phrase non-corrosive organic solvent as employed in certain of the following claims refers .to any organic solvent material unreactive with Z-SC:H4OC=H4Cl wherein Z represents a heterocyclic radical.

' 2. An insecticidal composition comprising as an active toxicant from 0.5 to 10 per cent by weight of a compound having the formula wherein R represents a cyclic organic radical selected from the group consisting or aromatic,

alicyclic, and heterocyclic radicals and in which any halogen substituents which may be present are attached directly to nuclear carbon atoms, n is an integer from 2 to 4, inclusive, and m is an integer not greater than 3.

3. An insecticidal composition comprising as.

an active toxicant from 0,5 to 10 per cent by weight of a compound having the formula wherein R represents a cyclic organic radical an active toxicant from 0.5 to 10 per :cent by weight of a compound the formula R-S-Cflt-O-Cnfil-Cl wherein It represents acyclic organic radical selected from the group consisting of aromatic, alicyclic, and heterocyclic radicals and in which any halogen substituents which may be present are attached directly to nuclear carbon atoms.

6. An insecticidal composition comprising as an active toxicant from 0.5 to 10 per cent by weight of a compound having the formula A-SC2H4OC2H4-Cl wherein A represents an aromatic radical of the "benzene series and in which any halogen substituents which may be present are attached directly to nuclear carbon atoms.

GERALD H. COLEMAN. CLARENCE n MOYLE, 

